The present invention relates to compounds of formulae I and II, which are suitable as ash-free antiwear additives and antioxidants, to lubricant compositions comprising compounds of formulae I and II as well as to their use.
For operating combustion engines, it is necessary to use lubricants having a low metal content and, therefore, a low ash content and, in view of exhaust gas catalyst compatibility, also a low phosphorus content. This invention therefore has for its object to provide metal-free and phosphorus-free additives or additive combinations which approach the good antioxidative and wear protection of the zinc dialkyldithiophosphates used to date.
U.S. Pat. No. 3,591,475 describes the preparation of asymmetrical dithioethers of the general formula 
by addition of a mercaptan Rxe2x80x2SH to an allyl sulfide (RSxe2x80x94CH2CHxe2x95x90CH2). The definitions of R and Rxe2x80x2 include numerous substituents of different structures. There is no description given of a dithioether containing a heterocyclic radical as a defined single compound. Benzothiazolyl is only mentioned as an example in the sense of an enumeration. The use of the compounds described in U.S. Pat. No. 3,591,475 is also disclosed unspecifically. Their suitability as agrochemicals having antiparasitic properties is mentioned there. In addition, these compounds are said to be suitable as stabilisers for polyolefins and also as additives for lubricants.
The preparation of benzothiazolyl dithioethers of formula 
with herbicidal activity is described on page 1847 of the English translation of Syntheses on the Basis of 2-benzothiazolylvinyl Sulfide, Zhurnal Organicheskoi Khimii, Vol. 2, No. 10, pp. 1883-1891, October 1966.
U.S. Pat. No. 5,258,258 describes processing solutions for the development of lithographic printing plates, which comprise thiadiazolyl dithioethers of formula 
U.S. Pat. No. 5,051,198 describes reaction products which are obtainable by reacting mercaptans with xcex2-thiodialkanols. These reaction products can be used as antioxidants.
This invention relates to compounds of formulae I and II described hereinafter, which are suitable as improved ash- and phosphorus-free antiwear additives and which additionally have an antioxidative effect: 
wherein
R1 is hydrogen or C1-C20alkyl;
R2 is a substituent from the group consisting of C1-C20alkyl, C5-C12cycloalkyl, C7-C12bicycloalkyl, phenyl, C7-C18alkylphenyl, naphthyl and C7-C9phenylalkyl, which substituent may be substituted by one or more than one substituent from the group consisting of amino, carboxy and hydroxy and/or may be interrupted by one or more than one bivalent radical from the group consisting of xe2x80x94Oxe2x80x94, xe2x80x94NR6xe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94NR6xe2x80x94 and xe2x80x94NR6xe2x80x94C(xe2x95x90O)xe2x80x94;
R3 and R4 are hydrogen or have the meanings of R2, with the proviso that R2 is C4-C20alkyl if
R3 and R4 are hydrogen;
R5 is hydrogen or groups of the partial formula 
wherein R2, R3 and R4 have the cited meanings or have the meaning of R2;
and R6 is hydrogen or C1-C4alkyl.
The compounds of formulae I and II are particularly suitable as multifunctional antiwear additives with additional antioxidative effect for lubricants, gear oils, hydraulic and metal working fluids as well as for greases. They are substantially ash- and phosphorus-free.
The definitions and terms used within the scope of the description of this invention preferably have the following meanings:
Examples of C1-C20alkyl are methyl, ethyl, n- or isopropyl or n-, sec- or tert-butyl and also straight-chain or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl, typically isooctyl or tert-nonyl. Examples of C5-C12cycloalkyl are cyclopentyl or cyclohexyl. Examples of C7-C12bicycloalkyl are e.g. bornyl or norbornyl. Examples of C7-C18alkylphenyl are phenyl which is substituted by mono-, di- or trimethyl. Examples of C7-C9phenylalkyl are e.g. benzyl or 2-phenylethyl.
In another of its aspects, this invention also relates to compounds of formulae I and II including all cases of isomerism, for example bond isomers or stereoisomers, resulting from the presence of a chiral centre. These cases of isomerism encompass optically pure enantiomers, diastereomers as well as racemic mixtures.
Preferred compounds are those of formulae I and II described above, wherein R1 is hydrogen; R2 is a substituent from the group consisting of C1-C20alkyl, phenyl, C7-C18-alkylphenyl and C7-C9phenylalkyl, which substituent may be substituted by one or more than one substituent from the group consisting of amino, carboxy and hydroxy and/or may be interrupted by one or more than one bivalent radical from the group consisting of xe2x80x94Oxe2x80x94, xe2x80x94NR6xe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94Oxe2x80x94, xe2x80x94Oxe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94NR6xe2x80x94 and xe2x80x94NR6xe2x80x94C(xe2x95x90O)xe2x80x94;
R3 and R4 are hydrogen or have the meaning of R2, with the proviso that R2 is C4-C20alkyl if
R3 and R4 are hydrogen;
R5 has the meanings of R2 or is groups of the partial formulae (A) and (B), wherein R2, R3 and R4 have the cited meanings; and R6 is hydrogen or alkyl.
Particularly preferred compounds are those of formulae I and II, wherein
R1 is hydrogen; R2 is a substituent from the group consisting of C1-C20alkyl, phenyl, C7-C18-alkylphenyl and C7-C9phenylalkyl, which substituent may be interrupted by one or more than one bivalent radical from the group consisting of xe2x80x94Oxe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94Oxe2x80x94 and xe2x80x94Oxe2x80x94C(xe2x95x90O)xe2x80x94;
R3 and R4 are hydrogen or have the meanings of R2, with the proviso that R2 is C4-C20alkyl if R3 and R4 are hydrogen;
R5 has the meanings of R2 or is groups of the partial formulae (A) and (B), wherein R2, R3 and R4 have the cited meanings.
Very particularly preferred objects of this invention are compounds of formulae I and II,
wherein R1 is hydrogen; R2 is C1-C20alkyl which may be interrupted by a bivalent radical from the group consisting of xe2x80x94Oxe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94Oxe2x80x94 and xe2x80x94Oxe2x80x94C(xe2x95x90O)xe2x80x94;
R3 and R4 are hydrogen or have the meanings of R2, with the proviso that R2 is C4-C20alkyl if
R3 and R4 are hydrogen;
R5 has the meanings of R2 or is groups of the partial formulae (A) and (B), wherein R2, R3 and R4 have the cited meanings.
Particularly preferred compounds are those of formula 
wherein R2 is C4-C18alkoxycarbonylmethyl, R3 is C4-C18alkoxycarbonylmethylthiomethyl and R4 is hydrogen; or
R2 is C5-C12alkyl, R3 is C5-C12alkylthiomethyl and R4 is hydrogen; or
R2 is C4-C18alkoxycarbonylmethyl, R3 is hydrogen and R4 is C4-C18alkoxycarbonylmethylthiomethyl; or
R2 is C5-C12alkyl, R3 is hydrogen and R4 is C5-C12alkylthiomethyl, and compounds of formula: 
wherein R2 and R2xe2x80x2 are C4-C18alkoxycarbonylmethyl, R3 and R3xe2x80x2 are C4-C18alkoxycarbonylmethylthiomethyl, and R4 and R4xe2x80x2 are hydrogen; or
R2 and R2xe2x80x2 are C5-C12alkyl, R3 and R3xe2x80x2 are C5-C12alkylthiomethyl and R4 and R4xe2x80x2 are hydrogen; or
R2 and R2xe2x80x2 are C4-C18alkoxycarbonylmethyl, R3 and R3xe2x80x2 hydrogen and R4 and R4xe2x80x2 are C4-C18alkoxycarbonylmethylthiomethyl; or
R2 and R2xe2x80x2 are C5-C12alkyl, R3 and R3xe2x80x2 are hydrogen and R4 and R4xe2x80x2 are C5-C12alkylthiomethyl.
Especially preferred are compounds of formula Ixe2x80x2,
wherein R2 is isooctyloxycarbonylmethyl, R3 is isooctyloxycarbonylmethylthiomethyl and R4 is hydrogen; or
R2 is tert-nonyl, R3 is tert-nonylthiomethyl and R4 is hydrogen; or
R2 is isooctyloxycarbonylmethyl, R3 is hydrogen and R4 is isooctyloxycarbonylmethylthiomethyl; or
R2 is tert-nonyl, R3 is hydrogen and R4 is tert-nonylthiomethyl, and also compounds of formula IIxe2x80x2,
wherein R2 and R2xe2x80x2 are isooctyloxycarbonylmethyl, R3 and R3xe2x80x2 are isooctyloxycarbonylmethylthiomethyl and R4 and R4xe2x80x2 are hydrogen; or
R2 and R2xe2x80x2 are tert-nonyl, R3 and R3xe2x80x2 are tert-nonylthiomethyl and R4 and R4xe2x80x2 are hydrogen; or
R2 and R2xe2x80x2 are C5-C10isooctyloxycarbonylmethyl, R3 and R3xe2x80x2 are hydrogen and R4 and R4xe2x80x2 are isooctyloxycarbonylmethyl; or
R2 and R2xe2x80x2 are C5-C10tert-nonyl, R3 and R3xe2x80x2 are hydrogen and R4 and R4xe2x80x2 are tert-nonylthiomethyl.
This invention furthermore relates to compositions with lubricants comprising a compound of formula I or II or mixtures thereof in combination with a base oil of lubricating viscosity or with fuels.
This invention also relates to a process for improving the performance properties of lubricants or lubricating greases, such as motor oil, turbine oil, gear oil, hydraulic or metal working fluids or liquid fuels, e.g. diesel or carburettor fuels, which comprises adding at least one compound of formula I or II to achieve a friction-reducing and/or antioxidative effect. Accordingly, this invention also relates to the use of compounds of formula I or II as additives in lubricants or lubricating greases, such as motor oils, turbine oils, gear oils, hydraulic fluids, metal working fluids, lubricating greases or diesel or carburettor fuels.
A base oil of lubricating viscosity can be used for the preparation of lubricating greases or lubricants, metal working, gear or hydraulic fluids.
Such lubricating greases or lubricants, metal working, gear and hydraulic fluids are based, for example, on mineral or synthetic lubricants or oils or on mixtures thereof. The skilled person is familiar with them, and they are described in the relevant literature, for example in Chemistry and Technology of Lubricants; Mortier, R. M. and Orszulik, S. T. (Editors); 1992 Blackie and Son Ltd. for GB, VCH-Publishers N. Y. for U.S., ISBN 0-216-92921-0, see pages 208 et seq. and 269 et seq.; in Kirk-Othmer Encyclopedia of Chemical Technology, fourth Edition 1969, J. Wiley and Sons, New York, Vol. 13, page 533 et seq. (Hydraulic Fluids); Performance Testing of Hydraulic Fluids; R. Tourret and E. P. Wright, Hyden and Son Ltd. GB, on behalf of The Institute of Petroleum London, ISBN 0 85501 317 6; Ullmann""s Encyclopedia of Ind. Chem., Fifth Completely revised Edition, Verlag Chemie, DE-Weinheim, VCH-Publishers for U.S., Vol. A 15, page 423 et seq. (lubricants), Vol. A 13, page 165 et seq. (hydraulic fluids).
The lubricants are preferably oils and greases, based e.g. on a mineral oil. Oils are preferred.
Another group of lubricants which may be used are vegetable or animal oils, fats, tallows and waxes or their mixtures with each other or their mixtures with the mentioned mineral or synthetic oils. Vegetable and animal oils, fats, tallows and waxes are, for example, palmnut oil, palm oil, olive oil, beet oil, rapeseed oil, linseed oil, groundnut oil, soybean oil, cottonseed oil, sunflower oil, pumpkin seed oil, coconut oil, corn oil, castor oil, walnut oil and mixtures thereof, fish oils, tallows of slaughter animals, such as beef tallow, neat""s foot oil and bone fat as well as their modified epoxidised and sulfoxidised forms, for example epoxidised soybean oil.
Examples of synthetic lubricants include lubricants based on aliphatic or aromatic carboxylates, polymeric esters, polyalkylene oxides, phosphates, poly-xcex1-olefins or silicones, on a diester of divalent acids with a monovalent alcohol, e.g. dioctyl sebacate or dinonyl adipate, on a triester of trimethylolpropane with a monovalent acid or with a mixture of such acids, e.g. trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures thereof, on a tetraester of pentaerythritol with a monovalent acid or with a mixture of such acids, e.g. pentaerythritol tetracaprylate, or on a complex ester of monovalent and divalent acids with polyvalent alcohols, for example a complex ester of trimethylolpropane with caprylic and sebacic acid or of a mixture thereof. Particularly suitable are, besides mineral oils, e.g. poly-xcex1-olefins, ester-based lubricants, phosphates, glycols, polyglycols and polyalkylene glycols and their mixtures with water.
Metal working fluids and hydraulic fluids can be prepared on the basis of the same substances as those described above for the lubricants. They are often also emulsions of such substances with water or other liquids.
The lubricant compositions of this invention are used, for example in combustion engines, e.g. in motor vehicles equipped e.g. with engines of the Otto, diesel, two-stroke, Wankel or orbital type.
The compounds of formula I or II are readily soluble in lubricants, in metal working and hydraulic fluids and are therefore particularly suitable as additives for lubricants, metal working and hydraulic fluids.
The compositions expediently comprise 0.005 up to 10.0% by weight of the compounds of formula I or II, preferably 0.01-5.0% by weight, more preferably 0.01-0.9% weight.
The compounds of formula I or II can be admixed to the lubricants in a manner known per se. The compounds are readily soluble for example in oleophilic solvents, e.g. in oils. They can also be used together with additional additives to prepare a concentrate or a so-called additive packet which, depending on the consumption, can be diluted to the concentrations to be used for the corresponding lubricant.
The lubricants, metal working and hydraulic fluids can additionally contain further additives which are added to further improve their basic properties. These additives include: additional antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour point depressants, dispersants, detergents, other extreme pressure additives, antiwear additives and friction reducers. Where appropriate, these additives can act synergistically with each other or with the novel compounds. Such additives are added in the usual amounts ranging from about 0.01 to 10.0% by weight each. Should it still be necessary to add phosphorus- or metal-containing additives, then these additives are preferably added in small amounts, for example of about 0.01 to 0.5% by weight.
Examples of further additives are:
Examples of phenolic antioxidants:
1.1 Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1xe2x80x2-methylundec-1xe2x80x2-yl)phenol, 2,4-dimethyl-6-(1xe2x80x2-methylheptadec-1xe2x80x2-yl)phenol, 2,4-dimethyl-6-(1xe2x80x2-methyltridec-1xe2x80x2-yl)phenol and mixtures thereof.
1.2 Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
1.3 Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tertbutyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
1.4 Tocopherols, xcex1-, xcex2-, xcex3-, xcex4-tocopherol and mixtures thereof (vitamin E).
1.5 Hydroxylated thiodiphenyl ethers, for example 2,2xe2x80x2-thiobis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-thiobis(4-octylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-3-methylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-2-methylphenol), 4,4xe2x80x2-thiobis(3,6-di-sec-amylphenol), 4,4xe2x80x2-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.
1.6 Alkylidenebisphenols, for example 2,2xe2x80x2-methylenebis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-methylenebis(6-tert-butyl-4-ethylphenol), 2,2xe2x80x2-methylenebis[4-methyl-6-(xcex1-methylcyclohexyl)-phenol], 2,2xe2x80x2-methylenebis(4-methyl-6-cyclohexylphenol), 2,2xe2x80x2-methylenebis(6-nonyl-4-methylphenol), 2,2xe2x80x2-methylenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2xe2x80x2-methylenebis[6-(xcex1-methylbenzyl)-4-nonylphenol], 2,2xe2x80x2-methylenebis[6-(xcex1,xcex1-dimethylbenzyl)-4-nonylphenol], 4,4xe2x80x2-methylenebis-(2,6-di-tert-butylphenol), 4,4xe2x80x2-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3xe2x80x2-tert-butyl-4xe2x80x2-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1.7 O-, N- and S-benzyl compounds, for example 3,5,3xe2x80x2,5xe2x80x2-tetra-tert-butyl-4,4xe2x80x2-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8 Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9 Aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10 Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)-isocyanurate.
1.11 Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12 Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13 Esters of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14 Esters of xcex2-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,Nxe2x80x2-bis (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.15 Esters of xcex2-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16 Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17 Amides of xcex2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants: for example N,Nxe2x80x2-di-isopropyl-p-phenylenediamine, N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, N,Nxe2x80x2-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-methylheptyl)-p-phenylenediamine, N,Nxe2x80x2-dicyclohexyl-p-phenylenediamine, N,Nxe2x80x2-diphenyl-p-phenylenediamine, N,Nxe2x80x2-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1-methylheptyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-cyclohexyl-Nxe2x80x2-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,Nxe2x80x2-dimethyl-N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,pxe2x80x2-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4xe2x80x2-diaminodiphenylmethane, 4,4xe2x80x2-diaminodiphenylmethane, N,N,Nxe2x80x2,Nxe2x80x2-tetramethyl-4,4xe2x80x2-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1xe2x80x2,3xe2x80x2-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyl-diphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- und dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N,N,Nxe2x80x2,Nxe2x80x2-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin4-ol.
Examples of other antioxidants:
Aliphatic or aromatic phosphites, esters of thiodipropionic acid or of thiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid, 2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,11-trithiatridecane and 2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane.
Examples of metal deactivators, for example for copper, are:
a) Benzotriazoles and the derivatives thereof, for example 2-mercaptobenzotriazole, 2,5-dimercaptobenzotriazole, 4- or 5-alkylbenzotriazoles (e.g. tolutriazole) and the derivatives thereof, 4,5,6,7-tetrahydrobenzotriazole and 5,5xe2x80x2-methylenebisbenzotriazole; Mannich bases of benzotriazole or tolutriazole, e.g. 1-[bis(2-ethylhexyl)aminomethyl)tolutriazole and 1-[bis(2-ethylhexyl)aminomethyl)benzotriazole; and alkoxyalkylbenzotriazoles such as 1-(nonyloxymethyl)benzotriazole, 1-(1-butoxyethyl)benzotriazole and 1-(1-cyclohexyloxybutyl)tolutriazole.
b) 1,2,4-Triazoles and the derivatives thereof, for example 3-alkyl(or aryl)-1,2,4-triazoles, and Mannich bases of 1,2,4-triazoles, such as 1-[bis(2-ethylhexyl)aminomethyl-1,2,4-triazole; alkoxyalkyl-1,2,4-triazoles such as 1-(1-butoxyethyl)-1,2,4-triazole; and acylated 3-amino-1,2,4-triazoles.
c) Imidazole derivatives, for example 4,4xe2x80x2-methylenebis(2-undecyl5-methylimidazole) and bis[(N-methyl)imidazol-2-yl]carbinol octyl ether.
d) Sulfur-containing heterocyclic compounds, for example 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and derivatives thereof; and 3,5-bis[di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazolin- 2-one.
e) Amino compounds, for example salicylidenepropylenediamine, salicylaminoguanidine and the salts thereof.
Examples of rust inhibitors are:
a) Organic acids, their esters, metal salts, amine salts and anhydrides, for example alkyl- and alkenylsuccinic acids and their partial esters with alcohols, diols or hydroxycarboxylic acids, partial amides of alkyl- and alkenylsuccinic acids, 4-nonylphenoxyacetic acid, alkoxy- and alkoxyethoxycarboxylic acids such as dodecyloxyacetic acid, dodecyloxy(ethoxy)acetic acid and the amine salts thereof, and also N-oleoylsarcosine, sorbitan monooleate, lead naphthenate, alkenylsuccinic anhydrides, for example dodecenylsuccinic anhydride, 2-(2-carboxyethyl)-1-dodecyl-3-methylglycerol and the salts thereof, in particular the sodium salts and triethanolamine salts.
b) Nitrogen-containing compounds, for example:
i. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, for example oil-soluble alkylammonium carboxylates, and also 1-[N,N-bis(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol.
ii. Heterocyclic compounds, for example: substituted imidazolines and oxazolines, and 2-heptadecenyl-1-(2-hydroxyethyl)imidazoline.
c) Phosphorus-containing compounds, for example: Amine salts of phosphoric acid partial esters or phosphonic acid partial esters, and zinc dialkyldithiophosphates.
d) Sulfur-containing compounds, for example: barium dinonylnaphthalenesulfonates, calcium petroleum sulfonates, alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic 2-sulfocarboxylic acids and the salts thereof.
e) Glycerol derivatives, for example: glycerol monooleate, 1-(alkylphenoxy)-3-(2-hydroxyethyl)glycerol, 1-(alkylphenoxy)-3-(2,3-dihydroxypropyl)glycerol and 2-carboxyalkyl-1,3-dialkylglycerol.
Examples of viscosity index improvers are:
Polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene/acrylate copolymers and polyethers.
Examples of pour-point depressants are:
Poly(meth)acrylates, ethylene/vinyl acetate copolymer, alkyl polystyrenes, fumarate copolymers, alkylated naphthalene derivatives.
Examples of dispersants/surfactants are:
Polybutenylsuccinic amides or -imides, polybutenylphosphonic acid derivatives and basic magnesium, calcium and barium sulfonates and basic magnesium, calcium and barium phenolates.
Examples of extreme pressure and antiwear additives are:
Sulfur- and/or phosphorus- and/or halogen-containing compounds, for example chlorinated paraffins, sulfurised olefins or vegetable oils (soybean oil and rapeseed oil), alkyl- or aryl-di- or -trisulfides, zinc dialkyldithiophosphates, such as zinc-bis(2-ethylhexyl)dithiophosphate, zinc dithiocarbamates, such as zinc diamyldithiocarbamate, molybdenum phosphorodithioates, molybdenum dithiocarbamates, triarylphosphates, such as tripolyphosphate, tricresylphosphate, isopropyl phenylphosphate, amine salts of mono- or dialkylphosphoric acids, e.g. the amine salts of mono/di-hexylphosphate, amine salts of alkylphosphonic acids, such as the amine salt of methylphosphonic acid, triaryl phosphites, e.g. tris[nonylphenyl]phosphite, dialkyl phosphites, such as dioctyl phosphite, triaryl monothiophosphates, e.g. triphenyl thiophosphate or tris-[isononylphenyl]thionophosphate or tert-butylated triphenyl thionophosphates, substituted trialkyl mono- or dithiophosphates, for example [(diisopropoxyphosphinothioyl)thio]propionate or butylene-1,3-bis[(diisobutoxyphosphinothioyl)propionate], trithiophosphates, such as trithiophosphoric acid, S,S,S-tris(isooctyl-2-acetate), amine salts of 3-hydroxy-1,3-thiaphosphetane-3-oxide, benzotriazoles or the derivatives thereof, e.g. bis(2-ethylhexyl)aminomethyltolutriazole, dithiocarbamates, such as methylene-bis-dibutyldithiocarbamate, derivatives of 2-mercaptobenzothiazole, e.g. 1-[N,N-bis(2-ethylhexyl)amino-methyl]-2-mercapto-1H-1,3-benzothiazole, derivatives of 2,5-dimercapto-1,3,4-thiadiazole, such as 2,5-bis(tert-nonylditdithio)-1,3,4-thiadiazole.
Examples of frictional coefficient reducers are, for example, lard oil, oleic acid, tallow, rapeseed oil, sulfurised fats, amines. Other examples are cited in EP-A-565487.
Examples of special additives for use in water/oil metal working and hydraulic fluids are:
Emulsifiers: petroleum sulfonates, amines, such as polyethoxylated fatty amines, nonionic surface active substances; buffers: alkanolamines; biocides: triazines, thiazolinones, trisnitromethane, morpholine, sodium pyridene ethol; processing speed improvers: calcium sulfonates and barium sulfonates;
Examples of fuel additives:
Such additives are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 12, 1994. They are mainly gasoline and diesel additives:
Gasoline: aminic antioxidants, in particular para-phenylenediamines, or phenolic antioxidants, e.g. 2,6-di-tert-butylphenol (as described above); metal deactivators, in particular N,Nxe2x80x2-disalicylidene-1,2-propane, benzotriazole, EDTA; rust inhibitors, for example carboxylic acids, sulfonates, amines or amine salts; dispersants, e.g. esters, amines of high molecular weight, Mannich bases, succinimides, boronated succinimides; detergents, for example fatty acid amides, non-polymeric amines, polybutene succinimides, polyether amines, low molecular weight amines, sulfonates, salicylic acid derivatives; demulsifiers, for example long-chain alcohols or phenols containing polyethylene or polybutylene groups; antiknock additives, for example manganese methylcyclopentadienyltricarbonyl, oxygen compounds, e.g. esters of vegetable oils, ethers, alcohols for improving the burning behaviour.
Diesel fuels: ignition improvers (cetane improvers), e.g. alkyl nitrates, ether nitrates, alkyl di-glycol nitrates, organic peroxides; stabilisers, in particular for cracked diesel: amines and other N-containing compounds which act as radical interceptors; rust inhibitors, as described above; detergents as described above; oxygen compounds as described above; cold flow improvers, i.e. for example pour point depressants (see above), cloud point depressants or so-called operability additives (OA), which are polymeric multicomponent systems improving, inter alia, the filter flow behaviour.
Preparation process:
The compounds of formulae I and II can be obtained in a manner known per se, for example by reacting a 2-mercaptobenzothiazole of formula 
or with a reactive functional derivative thereof, or a 2,5-dimercaptothiadiazole of formula 
with the alcohol of the above formula or with an alcohol R5xe2x80x94OH or with a reactive functional derivative thereof, with separation of water, preferably under acid conditions.